Condensation product of alpha, beta disubstituted acroleins with primary aromatic amines



Patented Dec. 1, 1931 UNITED STATES PATENT OFFICE WALTER KROPP, OE ELBEREELD, GERMANY, ASEIGNOR TO I. G. FARIBENINDUSTRIE AKTIENGESELLSGHAFT, OF FRANKFORT-ON-THE-MAIN, GERMANY, A CORPORA- TION 0F GERMANY CONDENSATION ZERODUGT OF ALPHA, BETA DISUBSTITUTED ACROLEINS WITH PRI- MARY AROMATIC .AMINES NoDravving. Application filed September 1/1928, Serial No. 303,615, and in Germany August 6, 1925.

The present invention relates to the manufacture of technically valuable compounds obtainable by condensing alphabeta-substituted acroleins with primary aromatic amines. 1

"Inaccordance with the invention analpha-beta-substituted acrolein, more particularly an aerolein of the general formula wherein R means alkyl, and R stands for alkyl or phenyl, is caused to be reacted upon by a primary aromatlc amine as for instance aniline, metaor para-toluidine, alpha-naphthyl-amine etc. in the presence'of a compound of an organic or morganic acid whereby these compounds will probably exert condensing properties.

The reaction may advantageously be performed with molecular quantitities of aldehyde and'amine but in many cases it will be of advantage to work with an excess of the aldehyde, which excess can easily be removed after the condensation according to known methods. The reaction already begins at room temperature and is in the most cases highly exothermic, so that an external heating, will beunnecessary but it may bementioned, that thebest results are obtained at temperatures between 90-120 C. and that the characterof thefinal products is somewhat dependent from the temperature employedas well as from the amount of the acidic substance used, Among the acidsubstancesI prefer fatty acids, especially those which. contain from '1 to 18 carbon atoms, as for instance formic acid, acetic acid, propionic acid, butyric acid, stearic acid etc., but

i'sto be understood that also the use of inorganic acids and other organicacids such as hydrochloric acid, 1 salicylic acid, cinnamic acid, aromatic sulfonic acids, oxalic acid, suc cinic'acid etc. is within the limits of my invention. The amount of acid advantageously themselves there may be used such substances as yield the aldehydes during the reaction,

such as the oximes of the aldehydes, products,

having the character of the corresponding aldoles and the like. Also it is possible to work in the presence of a suitable organic solvent, such asbenzene, toluene, etc., without departing from my invention.

The products thus obtainable form yellowish to reddish brown oils nearly insoluble in water, soluble in the usual organic solvents. They are excellent accelerators in vulcanization processes, especially in admixture with lamp black for instance gas lamp black. I do not know at present the exact structure of the new compounds but they probablyare formed by interaction of one mol of the aldehyde with one mol of the amine whereby water is eliminated. It may be stated that the new compounds described herein are not identical with the compounds obtainable from the same starting materials and according to the same process but without the addition of, an acid or with the addition of anotherecondensing agent. The difference in the properties of the products may e proved by the fact that thetensile strength of the 'materials obtained by the vulcanizadish" yellow n is thus'obtained nearlyin. 1

. of aniline are added.

. refluxing and is :Imainta'ined at this degree- -Efor- 343 hours,. care 'beingctaken that the 25 I water {formed during the reaction is allowed stances i-ret'urn zEO' .the reaction vessel.

used, the same may remain in the final prod uct as well as a part of the acid employed,

without diminishing the accelerating action;

Also when starting from an aldehyde in a rather impure state the final product will I 'To 8 parts-of formic acid 200 parts of alpha-ethyl-beta-propylacrolein (b. p. 17 2- 175? .C.) .andthen. .while stirring, .90 .parts the reaction mixturerises to about 50 C.

to separate. The temperature is caused' to :rise1to"1:10 interior temperature) while to distill off, while theother refluxing sub- Now :the ;--exce'ss of aldehyde and acid are removed :filtered, .A Slight yellow-oil is thus obtained,

' nearly insoluble in water, easily soluble in with 'acqueous sodium chloride solution and benzene, :benzine, acetic ester andthe like;

i Example 2 I A-crude a'lpha-ethyLbetapropylacrolein is prepared by stirring together 1 part of norm.

butylaldehyde and parts of soda 'lye (2%) Y at ordinary temperature until the *butylaldehyde has-disappeared, separating the reaction product from the soda lye, washing water and drying with anhydrous sodium sulfate. To 150 parts of this product9 parts of glacial acetic acid and "90 parts of .aniline are added. The t emperature soon beginsjto raise with separation of Water. IThetemperature is "maintained; at 105'1l5 C. I for hours and the reaction product further soluble in water, soluble in the usual organic solvents, exertinggstrong accelerating propf The temperature of lng hquorheated for a further 30 minutes 207 without .externaLheating while water begins [about 4' hours.

and .otherorganic solvents.

to 115120' C. (external temperature),

whereby water is allowed to distill ofi. The

remaining oily substance is now stirred with about 10% of fullers earth at about 70 (1.,

Example 4 7 2001521115 of crude alpha-ethyl-beta-propyl acrolein obtained as described in Example 2,

' are-mixed with '9-parts ofglacial acetic acid, anda-solution of 90-parts of aniline in 180 parts of benzene'is added. The mixture is heated to 80 C. for minutes, the benzene distilled ofl? after-that time and the remain,-

to 120C, Now the'excess of aldehyde and acid are remove'dfby steam distillation and the resulting oil is dried and distilled in 'vacuo @(8 mini). The-fraction distilling-over between -1'60.200 C. forms a yellowish toil,-

fwhiohgis insoluble in water, but soluble :in the usual organlc solvents, and showsrrespecially good properties ,as accelerator in. Vul- -canization vprocesses. rby steam-distillatiomsthe remaining :oil is I separated from theEwater while still warm. :anhydrous sodium sulfate is added and then Emmple 5 lein are mixed with 7 parts of glacial acetic acid.and.-90 parts-of aniline are added to this mixture at .room temperature. The mixture dried. The product, which. still contains ethylpropylsacrolein, may be used inthis state asa vulcanization accelerator.

Example 6 l 9 ipartslof stearic acid are dissolved in "100 :parts of.alphasethyl beta-propylsacrolein, parts of :aniline are added and the mixture 150 parts of alpha-ethyl-beta-propyl-acro-;

is heated to C. for threehours; Now" the excess of aldehyde is removed by steam distillation and the remainingoily substance dried bymeans of :anyhdrous sodiumsul falte. V Itforms a reddish oil, i=nsolub'le in water. 7

c mr 150 parts of alpha-ethyl-beta-propyl acrm acid, Into this mixture 51 parts of p, toluitemperature is still further maintained for The reaction mixture is now cooled, shaken with an, aqueous ammonia solutionand water and distilled in vacuoat :0. (external temperature) .until the -.c0mp onents of the mixture distilling over under these :jconditions are removed. It remains :an oil, soluble in benzene, acetone lein are mixed with 5 partse-f glacial acetic Ewample Example 9 Amixture of 126 grams of alpha-ethyl-betapropylacrolein 126 grams of alpha-napthylamine, 5 com. of glacial acetic acid and 800 ccm. of benzene is boiled for 6 hours on the waterv bath. Then the mixture is subjected to steam distillation and the remaining reddish brown oil is dried by means of anhydrous sodium sulfate.

v Example 10 13 parts of alpha-n-amyl-beta-phenylacrolein are mixed with 0.5 parts of glacial acetic acid and 5 parts of aniline, whereby self-heating and separation of water occurs.

The mixture is maintained for about 45- hours at a temperature of 105 (1, subjected to steam distillation, and the remaining substance dried by means of anhydrous sodium sulfate. It forms a yellowish oil insoluble in water. Instead of alpha-n-amyl-betaphenyl acrolein other acrolcins may be used for example alpha-isoproply-betadsobutylacrolein, alpha-methyl-beta-ethylacrolein and the like.

This is a continuation in part of my copending application Ser. No. 92,952, filed March 6th, 1926.

I claim 1. Process which comprises reacting upon an acrolein of the probable formulawherein R means alkyl, and stands for alkyl or phenyl, with a prlmary aromatic amine 1n the presence of an acid.

2. Process wh1ch comprises reacting upon an acroleln of the probable formula R: I 1 O on=oo wherein B means alkyl, and R stands for alkyl, or phcnyl with a primary aromatic amine in the presence of an organic: acid.

3. Process which comprises reacting upon an acrolein of the probable formula wherein? iR wmeans alkyl; and R stands for 1 alkyl;orwphenylg'fwith a primary aromatic amine in the presence of a fatty acidcontaining not more than 18 carbon atoms.

.L'Processwwhich comprises reacting upon ania'crol'ein of the probable formula I i514 Il11, p v p CH=OQV H p wherein R means alkyl, and R stands "for alkyl'or' phenyl; with afprima'ry aromatic amine at. a temperature between '120C. in the" presence of an organic acid in a quantity of 525% of the molar weight of the latter to each molar weight of the aldehyde applied.

5. Process which comprises reacting upon an acrolein of the probable formula III: l 0

CH=O-C H wherein R means alkyl, and R stands for alkyl or phenyl, with a primary aromatic amine at a temperature between 90120 C.

. in the presence of a fatty acid containing not more than 18 carbon atoms in a quantity of 5-25% of the molar weight of the latter to each molar weight of the aldehyde applied.

6. Process which comprises reacting upon an acrolein of the probable formula wherein R means alkyl, and R represents an alkyl or phenyl radical at a temperature between 90-120 C. with a compound of the group consisting of aniline m-toluidine and p-toluidine in the presence of a fatty acid containing not more than 18 carbon atoms in a quantity of 525% of the molecular weight of the latter to each molar weight of the aldehyde applied.

7. Process which comprises reacting upon 150 parts by weight of crude alpha-ethylbetaqn'opyl-acrolein with 90 parts by weight of aniline at a temperature of 115 C. in the presence of 9 parts by weight of glacial acetic acid for 33 hours, removing the excess of aldehyde separating the remaining oil, and drying it.

8. The new products obtainable according to the process claimed in claim 1, which prodnets are yellowish to reddish-brown oils nearly insoluble in water, soluble in the usual organic solvents and being accelerators in vulcanizing processes.

9. The new products obtainable according to the process claimed in claim 4, which prod nets are yellowish to reddish-brown oils nearly insoluble in water soluble in the usual organic solvents and being accelerators in vulcanizing processes.

to the process claimed in claim 6, which prodnets are yellowish to reddish-brown 'oils near- 1y insoluble in Water, soluble in 'the usu a1 I orgamc solvents' and being accelerators 1n vulcanizing. processes." I 11. The new product obtainable according 'to the process claimed in claim 7 which prodnot forms a reddish yellow oil nearly insoluble in Water, soluble inthe usual organic solvents, exerting strong accelerating properties in vulcanization processes.

V whereof ve hereunto sot o d 7 my hand. 1 I

-, 'WALTEB KRQ P; L1 8.]

CERTIFICATE OF CORRECTION.

Patent No. 1,834,849 Granted December 1, 1931, to

WALTER KROPP.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line 26, after "methods." insert the sentence It is to be understood that one molecule of the aldehyde reacts with one molecule of the amine regardless of the proportions used; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed, this 9th day of February, A. D. 1932.

M. J. Moore,

(Seal) Acting Commissioner of Patents. v 

